CN113816895B - Aromatic amine compounds, mixtures, compositions and organic electronic devices - Google Patents

Aromatic amine compounds, mixtures, compositions and organic electronic devices Download PDF

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CN113816895B
CN113816895B CN202110146813.1A CN202110146813A CN113816895B CN 113816895 B CN113816895 B CN 113816895B CN 202110146813 A CN202110146813 A CN 202110146813A CN 113816895 B CN113816895 B CN 113816895B
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aromatic amine
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CN113816895A (en
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谭甲辉
胡洁
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Abstract

The invention relates to aromatic amine compounds, mixtures, compositions and organic electronic devices containing spiro rings. The aromatic amine compound has a structure shown in a general formula (1), has higher electrochemical stability, and can improve the luminous efficiency and the service life of the device when being used as a hole transport material in an organic electronic device.

Description

Aromatic amine compounds, mixtures, compositions and organic electronic devices
Technical Field
The present invention relates to an aromatic amine compound, mixtures, compositions comprising the same, and organic electronic devices, particularly applications in organic light emitting diodes.
Background
Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and illumination due to the variety of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.
The organic electroluminescence refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic electroluminescent element utilizing the organic electroluminescent phenomenon generally has a structure in which a positive electrode and a negative electrode have an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent device, the organic layers have a multi-layered structure, and each layer contains a different organic material. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between two electrodes, holes are injected from a positive electrode into an organic layer, electrons are injected from a negative electrode into the organic layer, and when the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to a ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.
However, the light-emitting efficiency and the service life of the OLED device need to be further improved, because the OLED is operated as a current-driven device in a high current density state, and the materials are prone to joule heating, which results in degradation of the device, especially between the anode and the hole transport layer. The glass transition temperature of the common hole transport material is low, and the accumulation of joule heat causes the shape change of the film, and simultaneously accelerates the decomposition of the material, thereby influencing the service life of the device. In addition, the hole mobility of organic semiconductor materials is generally higher than the electron mobility, resulting in an imbalance in hole-electron transport that affects the light-emitting efficiency of the device.
At present, although a large number of hole transport materials have been developed, there are still a lot of problems how to design new materials with better performance to adjust, so as to achieve the effect of reducing the device voltage and improving the device efficiency and service life, which is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a novel class of aromatic amine compounds, which aims to solve the problems of low efficiency and lifetime of the existing organic electronic devices.
The technical scheme of the invention is as follows:
an aromatic amine compound represented by the general formula (1):
wherein:
x is selected from O, S or CR 1 R 2 ；
R 1 、R 2 Each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF 3 Cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having from 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, an aryloxy group having from 5 to 60 ring atoms, a heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;
r is independently selected from each occurrence: H. d, an alkyl group having 1 to 20C atoms, an amine group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, and at least one R is selected from the group consisting of formula (a):
l is selected from aromatic groups or heteroaromatic groups with the number of ring atoms of 6-40;
L 1 、L 2 、L 3 、L 4 each occurrence is independently selected from a single bond, an aromatic group or a heteroaromatic group with 6 to 40 ring atoms substituted or unsubstituted;
Ar 1 、Ar 2 、Ar 3 、Ar 4 each occurrence is independently selected from an aromatic group with 6-40 substituted or unsubstituted ring atoms, a heteroaromatic group with 5-40 substituted or unsubstituted ring atoms or a non-aromatic ring system;
* Representing the ligation site.
A mixture comprising an aromatic amine compound as described above, and at least one other organic functional material.
A composition comprising at least one aromatic amine compound as described above and at least one organic solvent.
An organic electronic device comprising a functional layer comprising or prepared from an aromatic amine compound or mixture as described above.
The beneficial effects are that:
the aromatic amine compound has higher electrochemical stability and stronger hole transport property, and can improve the luminous efficiency of a device and prolong the service life of the device when being used as a hole transport material.
Detailed Description
The invention provides an aromatic amine compound and application thereof in an organic electroluminescent device, an organic electronic device containing the compound and a preparation method thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.
In the present invention, aromatic groups and aromatic ring systems have the same meaning and can be interchanged.
In the present invention, the heteroaromatic groups, heteroaromatic groups and heteroaromatic ring systems have the same meaning and can be interchanged.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
"aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic species. For example, "a substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group having 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted. Suitable examples of aryl groups include, but are not limited to: benzene, biphenyl, terphenyl, naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted. Suitable examples of heteroaryl groups include, but are not limited to: triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, naphthyridine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, dibenzothiophene, dibenzofuran, carbazole, and derivatives thereof.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-eicosyl, N-docosanyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc.
The invention relates to an aromatic amine compound, which is shown in a general formula (1):
wherein:
x is selected from O, S or CR 1 R 2 ；
R 1 、R 2 Each occurrence is independently selected from: H. d, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF 3 Cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having from 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, an aryloxy group having from 5 to 60 ring atoms, a heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;
r is independently selected from each occurrence: H. d, an alkyl group having 1 to 20C atoms, an amine group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, and at least one R is selected from the group consisting of formula (a):
l is selected from aromatic groups or heteroaromatic groups with the number of ring atoms of 6-40;
L 1 、L 2 、L 3 、L 4 each occurrence is independently selected from a single bond, an aromatic group or a heteroaromatic group with 6 to 40 ring atoms substituted or unsubstituted;
Ar 1 、Ar 2 、Ar 3 、Ar 4 each occurrence is independently selected from an aromatic group with 6-40 substituted or unsubstituted ring atoms, a heteroaromatic group with 5-40 substituted or unsubstituted ring atoms or a non-aromatic ring system;
* Representing the ligation site.
In one example, X is selected from O or S;
in one example, X is selected from CR 1 R 2 ，R 1 、R 2 Each independently selected from H, D or a linear alkyl group having 1 to 20C atoms; further, R 1 、R 2 Selected from methyl groups.
In the present invention, the position of the spiro ring in the general formula (1) is defined as follows:
in one example, only one R in formula (1) is selected from formula a;
further, the general formula (1) is selected from the general formulae (2-1) or (2-2):
preferably, formula A in formula (1) is attached to the C atom at spiro-pass position 1.
Preferably, formula A in formula (1) is attached to the C atom at spiro-pass position 2.
Preferably, formula A in formula (1) is attached to the C atom at spiro-pass position 3.
Preferably, formula A in formula (1) is attached to the C atom at spiro-pass position 6.
Preferably, formula A in formula (1) is attached to the C atom at spiro-pass position 7.
In one embodiment, L is selected from an aromatic or heteroaromatic group having 6 to 30 ring atoms; further, L is selected from an aromatic group or a heteroaromatic group having 6 to 20 ring atoms; further, L is selected from an aromatic group or a heteroaromatic group having 6 to 15 ring atoms.
In one example, L is selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, pyridine, pyrimidine, triazine, fluorene, dibenzothiophene, silafluorene, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenylsilicon, spirofluorene, spirosilafluorene, and the like.
Further, L is selected from benzene, naphthalene, pyridine, pyrimidine, triazine.
Still further, the general formula (1) is selected from the general formulae (3-1) or (3-2):
in one embodiment, L 1 、L 2 、L 3 、L 4 Each occurrence is independently selected from a single bond, an aromatic group or a heteroaromatic group with 6 to 20 ring atoms substituted or unsubstituted; further, L 1 、L 2 、L 3 、L 4 Each occurrence is independently selected from a single bond and an aromatic group having 6 to 12 ring atoms.
In one example, an aromatic amine compound according to the present invention, wherein L 1 -L 4 Independently selected from a single bond or the following groups:
further, L 1 -L 4 Independently selected from a single bond or phenyl.
In an example, ar 1 -Ar 4 Independently selected from the following groups:
wherein:
X 1 each occurrence is independently selected from N or CR 3 ；
Each occurrence of Y is independently selected from O, S, S = O, SO 2 、NR 4 、PR 4 、CR 4 R 5 Or SiR 4 R 5 ；
R 3 、R 4 、R 5 Each occurrence is independently selected from: H. d, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF 3 Cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having from 5 to 20 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 20 ring atoms, an aryloxy group having from 5 to 20 ring atoms, a heteroaryloxy group having from 5 to 20 ring atoms, or a combination of these groups.
Further, ar 1 -Ar 4 Independently selected from the following groups:
wherein: o is selected from any integer from 0 to 7; p is selected from any integer from 0 to 9; q1 is selected from any integer from 0 to 4; q2 is selected from any integer from 0 to 3
Further, ar 1 -Ar 4 Independently selected from the following groups:
wherein: * Representing the ligation site.
In an example, ar 1 -Ar 4 Are respectively and independently selected from
In an example, ar 1 -Ar 4 At least one of them is selected fromFurther, ar 1 -Ar 4 At least two of them are selected from->
In an example, ar 1 -Ar 4 At least one of them is selected fromFurther, ar 1 -Ar 4 At least two of them are selected from->
Further, the method comprises the steps of,selected from->
In an example, ar 1 -Ar 4 At least one of them is selected fromFurther, ar 1 -Ar 4 At least two of them are selected from->
In an example, ar 1 -Ar 4 At least one of them is selected fromFurther, ar 1 -Ar 4 At least two of them are selected from->
In an example, ar 1 -Ar 4 At least one of them is selected fromFurther, ar 1 -Ar 4 At least two of them are selected from->Further, ar 1 -Ar 4 Are all selected from->
In one example, in the above formula-L 1 -Ar 1 and-L 3 -Ar 3 Selected from the same structures.
In one example, in the above formula-L 2 -Ar 2 and-L 4 -Ar 4 Selected from the same structures.
In one example, in the above formula-L 1 -Ar 1 and-L 3 -Ar 3 Selected from the same structure, and-L 2 -Ar 2 and-L 4 -Ar 4 Selected from the same structures.
In one example, formula (A) is selected from (B-1), (B-2), or (B-3):
wherein: ar in (B-1), (B-2) or (B-3) 2 And Ar is a group 4 Independently selected fromPreferably, R 3 Each occurrence is independently selected from: H. d, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or a phenyl group.
Further, L in (B-1), (B-2) or (B-3) 1 -L 4 Independently selected from a single bond or phenyl or naphthyl.
Further, the general formula (1) is selected from the following general formulae:
in one embodiment, formula (1) is selected from the following formulae:
wherein: r is R 3 Each occurrence is independently selected from: H. d, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or a phenyl group.
Further, the general formula (1) is selected from the following general formulae:
wherein: r is R 3 Each occurrence is independently selected from: H. d, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or a phenyl group.
Preferably, A in the above formular 2 And Ar is a group 4 Independently selected from phenyl, phenyl substituted with deuterium,L 2 、L 4 Independently selected from a single bond or phenyl or naphthyl.
Further, the general formula (1) is selected from the following general formulae:
preferably Ar in the above formula 2 And Ar is a group 4 Independently selected from phenyl, phenyl substituted with deuterium, L 2 、L 4 Independently selected from a single bond or phenyl.
In a preferred embodiment, an aromatic amine compound according to the present invention is preferably selected from, but not limited to, the following structures:
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the aromatic amine compound according to the present invention can be used as a functional material in a functional layer of an electronic device. Organic functional layers include, but are not limited to, hole Injection Layers (HIL), hole Transport Layers (HTL), electron Transport Layers (ETL), electron Injection Layers (EIL), electron Blocking Layers (EBL), hole Blocking Layers (HBL), light emitting layers (EML).
In one example, the aromatic amine compound according to the present invention is used in a hole transport layer.
The invention further relates to a mixture comprising at least one aromatic amine compound as described above and at least one further organic functional material selected from the group consisting of Hole Injection Materials (HIM), hole Transport Materials (HTM), electron Transport Materials (ETM), electron Injection Materials (EIM), electron Blocking Materials (EBM), hole Blocking Materials (HBM), luminescent materials (Emitter), host materials (Host) and organic dyes. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In one example, another organic functional material is selected from electron transport materials, as a co-host for use in electronic devices.
The invention also relates to a composition comprising at least one aromatic amine compound or mixture as described above, and at least one organic solvent; at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphate ester compound, or mixture of two or more solvents.
In a preferred embodiment, a composition according to the invention is characterized in that at least one organic solvent is selected from aromatic or heteroaromatic based solvents.
Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but are not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;
examples of aromatic ketone-based solvents suitable for the present invention are, but are not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;
examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;
in some preferred examples, the composition according to the invention, at least one of the solvents may be chosen from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In other preferred examples, the composition according to the invention, at least one solvent may be chosen from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particular preference is given to octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate.
The solvent may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one of the above-mentioned organic compounds or polymers or mixtures and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.
In some preferred examples, particularly suitable solvents for the present invention are solvents having Hansen (Hansen) solubility parameters within the following ranges:
δd (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0MPa 1/2;
δp (polar force) is in the range of 0.2 to 12.5MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2;
δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2.
The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably not less than 180 ℃; more preferably not less than 200 ℃; more preferably not less than 250 ℃; and most preferably at a temperature of 275 ℃ or more or 300 ℃ or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent system to form a film comprising the functional material.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The compositions according to the invention may comprise from 0.01 to 10% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 5% by weight, most preferably from 0.25 to 3% by weight, of a compound or mixture according to the invention.
The invention also relates to the use of the above-described composition as a coating or printing ink for the preparation of organic electronic devices, particularly preferably by printing or coating.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, spray Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, inkjet printing and inkjet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. The printing technology and the related requirements of the solution, such as solvent, concentration, viscosity and the like.
The invention also provides an application of the aromatic amine compound, the mixture or the composition in an organic electronic device, wherein the organic electronic device can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emitting diode (Organic Plasmon Emitting Diode) and the like, and particularly preferably an OLED. In the examples of the present invention, aromatic amine compounds are preferably used for the hole transport layer of the OLED device.
The invention further relates to an organic electronic device comprising at least one functional layer comprising one of the aromatic amine compounds, mixtures or prepared from the compositions described above. Further, an organic electronic device comprising a cathode, an anode and at least one functional layer comprising one or a mixture of the aromatic amine compounds described above or prepared from the composition described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emitting layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL); preferably, the functional layer is selected from hole transport layers.
In an embodiment, the organic electroluminescent device according to the present invention, the organic functional layer includes a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, and an electron transport layer; the first hole transport layer is above the hole injection layer, the second hole transport layer is above the first hole transport layer, the light emitting layer is above the second hole transport layer, and the electron transport layer is above the light emitting layer; the second hole transport layer contains the aromatic amine compound described above.
The organic electronic device may be selected from, but not limited to, organic Light Emitting Diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic Field Effect Transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light emitting field effect transistors.
The light-emitting device, especially the OLED, comprises a substrate, an anode, at least one light-emitting layer and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one example, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In some examples, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one example, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the light-emitting body in the light-emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
The light emitting device according to the present invention has a light emitting wavelength of 300 to 1200nm, preferably 350 to 1000nm, more preferably 400 to 900 nm.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The invention will be described in connection with preferred embodiments, but the invention is not limited to the embodiments described below, it being understood that the appended claims outline the scope of the invention and those skilled in the art, guided by the inventive concept, will recognize that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Synthesis of Compounds
Example 1: synthesis of Compound A
Synthesis of intermediate 3
Compound 1 (0.1 mol), compound 2 (0.2 mol), pd (dba) 2.72 g (0.003 mol), t-Bu3P17.2mL (0.009 mol), naOBu38.44g (0.4 mol) were dissolved in 500mL of anhydrous toluene at 90℃N 2 The reaction was stirred for 3 hours under an atmosphere. After the reaction, 500mL of water was added, extraction was performed with ethyl acetate, post-treatment water washing was performed, the organic phase was dried with anhydrous magnesium sulfate, filtered, the solvent was spin-dried, and separated and purified by silica gel chromatography, wherein the mobile phase was petroleum ether/dichloromethane mixed solvent (volume ratio=4:1) and petroleum ether was passed through a silica gel column, to obtain 48g of intermediate 3, with a yield of 80%. MS: m/z test value 598.37g/mol.
Synthesis of example A
Intermediate 3 (0.1 mol), compound 4 (0.1 mol), sodium carbonate 42.4g (0.4 mol), tetrakis triphenylphosphine palladium 6.93g (0.006 mol) were dissolved in 500mL of a mixed solvent (volume ratio=1:3), N at 90 ℃ 2 The reaction was stirred overnight under an atmosphere. Cooling to room temperature after the reaction, adding ethyl acetate for dilution extraction, drying the organic phase with anhydrous magnesium sulfate, suction filtering, spin-drying the solvent, separating and purifying by silica gel chromatography, wherein the mobile phase is petroleum ether/dichloromethane mixed solvent (volumeRatio = 2:1), 62g of example a were obtained, yield 68%. MS: m/z test value 911.18g/mol.
Example 2: synthesis of Compound B
Synthesis of intermediate 7
Compound 5 (0.1 mol), compound 6 (0.1 mol), pd (dba) 2.72 g (0.003 mol), t-Bu3P17.2mL (0.009 mol), naOBu19.22g (0.2 mol) were dissolved in 200mL of anhydrous toluene at 90℃N 2 The reaction was stirred for 3 hours under an atmosphere. After the reaction, 300mL of water was added, extraction was performed with ethyl acetate, and the organic phase was dried over anhydrous magnesium sulfate, filtered, the solvent was spin-dried, and separated and purified by silica gel chromatography, wherein the mobile phase was petroleum ether/dichloromethane mixed solvent (VPE: vdcm=1:2), to obtain 15.3g of intermediate 7 in 59% yield. MS: m/z test value 361.48g/mol.
Synthesis of intermediate 8
Similar to the synthesis procedure for intermediate 3, the difference is that compound 2 is replaced with compound 7, and finally intermediate 8 is obtained. MS: m/z test value 831.25g/mol.
Synthesis of example B
In analogy to the synthetic procedure of example a, the difference is that compound 3 is replaced by compound 8, compound 4 is replaced by compound 9, and finally example B is obtained. MS: m/z test value 939.15g/mol.
Example 3: synthesis of Compound C
Synthesis of intermediate 10
In analogy to the synthetic procedure of example a, intermediate 10 was finally obtained. MS: m/z test value 911.18g/mol.
Synthesis of intermediate 11
Intermediate 10 (0.1 mol), anhydrous DMF200 ml was added to the reactor, NBS (0.2 mol) was slowly added to the above solution and stirred overnight at room temperature. After the reaction, 1L of water was added to precipitate a solid, which was stirred for 30min, filtered, washed with water three times and dried to obtain 90.8g of intermediate 11 in 85% yield. MS: m/z test value 1068.97g/mol.
Synthesis of intermediate 12
100 ml of anhydrous THF (11) (0.05 mol) is added into a double-mouth reaction bottle with 250ml, nitrogen is replaced for five times, n-butyllithium (50 ml,0.12 mol) is dropwise added under the protection of nitrogen at-78 ℃, trimethyl borate (0.14 mol) is dropwise added after reaction for 1.5h at-78 ℃, the reaction is carried out at room temperature overnight, dilute hydrochloric acid is added for stirring for 30min, EA extraction, washing, drying, decompression concentration, an excessively rapid silica gel column, PE is eluted with impurities, EA is eluted out, and the product is evaporated to dryness under reduced pressure, thus 30g of intermediate 12 is obtained, and the yield is 61%. MS: m/z test value 998.81g/mol.
Synthesis of example C
Intermediate 12 (0.05 mol), compound 13 (0.12 mol), sodium carbonate 42.4g (0.4 mol), and tetrakis triphenylphosphine palladium 6.93g (0.006 mol) were dissolved in 500mL of a mixed solvent (volume ratio=1:3), and the reaction was stirred under an N2 atmosphere at 90 ℃ overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, ethyl acetate was added to dilute the mixture, the mixture was extracted, the organic phase was dried over anhydrous magnesium sulfate, and then, the mixture was suction-filtered, and after spin-drying the solvent, the mixture was separated and purified by silica gel chromatography, wherein the mobile phase was a petroleum ether/dichloromethane mixed solvent (volume ratio=1:1), to obtain 37g of example C, and the yield was 69%. MS: m/z test value 1073.44g/mol.
Example 4: synthesis of Compound D
Synthesis of intermediate 16
Similar to the synthesis procedure for intermediate 7, the difference is that intermediate 5 is replaced with intermediate 14, intermediate 6 is replaced with intermediate 15, and finally intermediate 16 is obtained. MS: m/z test value 361.49g/mol.
Synthesis of intermediate 17
Similar to the synthesis procedure for intermediate 3, the difference is that intermediate 2 is replaced with intermediate 16, and finally intermediate 17 is obtained. MS: m/z test value 831.50g/mol.
Synthesis of example D
In analogy to the synthesis procedure of example a, the difference is that intermediate 3 is replaced by intermediate 17 and intermediate 4 is replaced by intermediate 18, finally giving example D. MS: m/z test value 1143.51g/mol.
Example 5: synthesis of Compound E
Synthesis of intermediate 20
Similar to the synthesis procedure for intermediate 7, the difference is that intermediate 5 is replaced with intermediate 19, and finally intermediate 20 is obtained. MS: m/z test value 335.41g/mol.
Synthesis of intermediate 21
Similar to the synthesis procedure for intermediate 3, the difference is that intermediate 2 is replaced with intermediate 20, and intermediate 21 is finally obtained. MS: m/z test value 779.34g/mol.
Synthesis of example E
The procedure is analogous to the one for example A, except that intermediate 3 is replaced with intermediate 21 and intermediate 4 is replaced with intermediate 22, finally giving example E. MS: m/z test value 1091.34g/mol.
Example 6: synthesis of Compound F
Synthesis of intermediate 24
Similar to the synthesis procedure for intermediate 7, the difference is that intermediate 5 is replaced with intermediate 19, intermediate 6 is replaced with intermediate 23, and finally intermediate 24 is obtained. MS: test value 371.48g/mol.
Synthesis of intermediate 25
Similar to the synthesis procedure for intermediate 3, the difference is that intermediate 2 is replaced with intermediate 24, and finally intermediate 25 is obtained. MS: test value 851.49g/mol.
Synthesis of example F
Similar to the synthetic procedure of example a, except that intermediate 3 was replaced with intermediate 25, intermediate 4 was replaced with intermediate 26, and example F was finally obtained. MS: m/z test value 1173.52g/mol.
Example 7: synthesis of Compound G
Synthesis of intermediate 28
Similar to the synthesis procedure for intermediate 7, the difference is that intermediate 5 is replaced with intermediate 19, intermediate 6 is replaced with intermediate 27, and finally intermediate 28 is obtained. MS: test value 410.52g/mol.
Synthesis of intermediate 29
Similar to the synthesis procedure for intermediate 3, the difference is that intermediate 2 is replaced with intermediate 28, and finally intermediate 29 is obtained. MS: m/z test value 929.56g/mol.
Synthesis of example G
In analogy to the synthesis procedure of example a, the difference is that intermediate 3 is replaced by intermediate 29 and intermediate 4 is replaced by intermediate 30, finally giving example G. MS: m/z test value 1125.51g/mol.
Example 8: synthesis of Compound H
Synthesis of intermediate 37
Similar to the synthesis procedure for intermediate 7, the difference is that intermediate 5 is replaced with intermediate 19, intermediate 6 is replaced with intermediate 36, and finally intermediate 37 is obtained. MS: m/z test value 410.52g/mol.
Synthesis of intermediate 31
Similar to the synthesis procedure for intermediate 3, the difference is that intermediate 2 is replaced with intermediate 37, and intermediate 31 is finally obtained. MS: m/z test value 929.56g/mol.
Synthesis of example H
Similar to the synthetic procedure of example a, except that intermediate 3 was replaced with intermediate 31, intermediate 4 was replaced with intermediate 26, and example H was finally obtained. MS: m/z test value 1251.59g/mol.
Example 9: synthesis of Compound I
Synthesis of intermediate 32
Compound 7 (0.1 mol), compound 1 (0.1 mol), pd (dba) 2.72 g (0.003 mol), t-Bu3P17.2mL (0.009 mol), naOBu38.44g (0.4 mol) were dissolved in 500mL of anhydrous toluene, N at 90 ℃ 2 The reaction was stirred for 3 hours under an atmosphere. After the reaction, 500mL of water is added, the mixture is extracted with ethyl acetate, the water is subjected to post-treatment, the organic phase is dried with anhydrous magnesium sulfate, the solvent is dried by rotation after filtration, the solvent is separated and purified by a silica gel chromatography, the mobile phase is petroleum ether/dichloromethane mixed solvent (volume ratio=4:1), and petroleum ether passes through a silica gel column, and finally the intermediate 32 is obtained. MS: m/z test value 410.52g/mol.
Synthesis of intermediate 34
Similar to the synthesis procedure for intermediate 32, the difference is that intermediate 7 is replaced with intermediate 33, intermediate 1 is replaced with intermediate 32, and finally intermediate 34 is obtained. MS: m/z test value 929.56g/mol.
Synthesis of example H
Similar to the synthetic procedure of example a, except that intermediate 3 was replaced with intermediate 34, intermediate 4 was replaced with intermediate 35, and example H was finally obtained. MS: m/z test value 1251.59g/mol.
2. Preparation and characterization of OLED devices
The following describes in detail the preparation process of the OLED device by using the specific embodiment, and the structure of the red OLED device is as follows: ITO/HI/HT-1/HT-2/EML/ET: liq/Liq/Al.
a. Cleaning an ITO (indium tin oxide) conductive glass substrate: cleaning with various solvents (such as chloroform, acetone or isopropanol, or both), and performing ultraviolet ozone treatment;
b. vapor deposition: the ITO substrate was transferred into a vacuum vapor deposition apparatus under high vacuum (1X 10 -6 Mbar) a HI layer (compound HI) was formed with a thickness of 30nm using a resistance heating evaporation source, a first hole transport layer (compound HT-1) was formed on the HI layer by heating in sequence, followed by evaporation of a second hole transport layer (compound a) with a thickness of 10nm on the first hole transport layer. Subsequently RH is placed in one evaporation unit and compound RD is placed in another evaporation unit as dopant, allowing the material to evaporate at different rates, so that RH: RD is formed on the second hole transport layer at a weight ratio of 100:3 to form a 40nm light emitting layer. Then, ET and LiQ were put in different evaporation units, respectively, co-deposited at a ratio of 50 wt% to form an electron transport layer of 30nm on the light emitting layer, then, liQ of 1nm was deposited on the electron transport layer as an electron injection layer, and finally, al cathode of 100nm in thickness was deposited on the electron injection layer.
c. And (3) packaging: the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
Device examples 2-10 were prepared in the same manner as device example 1. The difference is that the second hole transport layer was selected from a different compound, as shown in table 1.
The device performance of the above examples and comparative examples was tested and is shown in table 1; wherein the driving voltage and current efficiency is 10mA/cm 2 Testing under current density; the device lifetime of T95 refers to a constant current density of 50mA/cm 2 The brightness decays to 95% time.
TABLE 1
Compared with device examples 10-13, the current efficiency and the service life of the device examples 1-9 are obviously improved, and the compound disclosed by the invention is applied to an OLED device, so that the current efficiency and the service life of the device can be improved, and meanwhile, the driving voltage of the device can be reduced.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (4)

1. An aromatic amine compound selected from any one of the following formulas:
wherein:
x is selected from O, S or CR 1 R 2 ；R 1 、R 2 Each occurrence is independently selected from: h or methyl;
L 1 、L 2 、L 3 、L 4 each occurrence is independently selected from a single bond or any of the following groups:
Ar 2 、Ar 4 each occurrence is selected from the following groups:
wherein each occurrence of Y is independently selected from O, S or CR 4 R 5 ；
R 3 Each occurrence is independently selected from: H. d, a linear alkyl group having 1 to 10C atoms or a branched alkyl group having 3 to 10C atoms;
R 4 、R 5 each occurrence is independently selected from H or methyl;
* Representing the ligation site.
2. A mixture comprising an aromatic amine compound according to claim 1 and at least one other organic functional material.
3. A composition comprising at least one aromatic amine compound according to claim 1 or a mixture according to claim 2, and at least one organic solvent.
4. An organic electronic device comprising a functional layer, wherein the functional layer comprises an aromatic amine compound according to claim 1 or a mixture according to claim 2 or is prepared from the composition according to claim 3.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109575037A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application
CN109574908A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application on organic electroluminescence device
CN109575038A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device
CN109804045A (en) * 2016-10-14 2019-05-24 罗门哈斯电子材料韩国有限公司 Organnic electroluminescent device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109804045A (en) * 2016-10-14 2019-05-24 罗门哈斯电子材料韩国有限公司 Organnic electroluminescent device
CN109575037A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application
CN109574908A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application on organic electroluminescence device
CN109575038A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device

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